Synthesis and Wittig rearrangement of 3- and 4-benzyloxyphenylphosphonamidates

Funding: We thank EPSRC(UK) and CRITICAT Centre for Doctoral Training for a studentship to R.A.I. (Grant EP/L016419/1).A series of seven O-ethyl-N-butylphenylphosphonamidates with benzyl ether substituents at the para or meta position have been prepared and fully characterised. Upon treatment with n-butyllithium in THF at RT, these undergo Wittig rearrangement in six cases to give the novel phosphonamidate-substituted diarylmethanols in moderate to good yield.Publisher PDFPeer reviewe

High Resolution Millimeter-Wave Mapping of Linearly Polarized Dust Emission: Magnetic Field Structure in Orion

We present 1.3 and 3.3 mm polarization maps of Orion-KL obtained with the BIMA array at approximately 4 arcsec resolution. Thermal emission from magnetically aligned dust grains produces the polarization. Along the Orion ``ridge'' the polarization position angle varies smoothly from about 10 degrees to 40 degrees, in agreement with previous lower resolution maps. In a small region south of the Orion ``hot core,'' however, the position angle changes by 90 degrees. This abrupt change in polarization direction is not necessarily the signpost of a twisted magnetic field. Rather, in this localized region processes other than the usual Davis-Greenstein mechanism might align the dust grains with their long axes parallel with the field, orthogonal to their normal orientation.Comment: AAS preprint:14 pages, 2 figures (3mm.eps and 1mm.eps); requires aaspp4.sty To be published in Astrophysical Journal Letter

Reactive oxygen species in spermatozoa: methods for monitoring and significance for the origins of genetic disease and infertility

Human spermatozoa generate low levels of reactive oxygen species in order to stimulate key events, such as tyrosine phosphorylation, associated with sperm capacitation. However, if the generation of these potentially pernicious oxygen metabolites becomes elevated for any reason, spermatozoa possess a limited capacity to protect themselves from oxidative stress. As a consequence, exposure of human spermatozoa to intrinsically- or extrinsically- generated reactive oxygen intermediates can result in a state of oxidative stress characterized by peroxidative damage to the sperm plasma membrane and DNA damage to the mitochondrial and nuclear genomes. Oxidative stress in the male germ line is associated with poor fertilization rates, impaired embryonic development, high levels of abortion and increased morbidity in the offspring, including childhood cancer. In this review, we consider the possible origins of oxidative damage to human spermatozoa and reflect on the important contribution such stress might make to the origins of genetic disease in our species

Polarization of Thermal Emission from Aligned Dust Grains Under an Anisotropic Radiation Field

If aspherical dust grains are immersed in an anisotropic radiation field, their temperature depends on the cross-sections projected in the direction of the anisotropy.It was shown that the temperature difference produces polarized thermal emission even without alignment, if the observer looks at the grains from a direction different from the anisotropic radiation. When the dust grains are aligned, the anisotropy in the radiation makes various effects on the polarization of the thermal emission, depending on the relative angle between the anisotropy and alignment directions. If the both directions are parallel, the anisotropy produces a steep increase in the polarization degree at short wavelengths. If they are perpendicular, the polarization reversal occurs at a wavelength shorter than the emission peak. The effect of the anisotropic radiation will make a change of more than a few % in the polarization degree for short wavelengths and the effect must be taken into account in the interpretation of the polarization in the thermal emission. The anisotropy in the radiation field produces a strong spectral dependence of the polarization degree and position angle, which is not seen under isotropic radiation. The dependence changes with the grain shape to a detectable level and thus it will provide a new tool to investigate the shape of dust grains. This paper presents examples of numerical calculations of the effects and demonstrates the importance of anisotropic radiation field on the polarized thermal emission.Comment: 13pages, 7figure

Impact of birth weight and gender on early postnatal hypothalamic energy balance regulatory gene expression in the young lamb

Peer reviewedPreprin

The risk of non-union per fracture:current myths and revised figures from a population of over 4 million adults

<p>Background and purpose — Fracture non-union remains a major clinical problem, yet there are no data available regarding the overall risk of fractures progressing to non-union in a large population. We investigated the rate of non-union per fracture in a large adult population.</p> <p>Methods — National data collected prospectively over a 5-year period and involving just under 5,000 non-unions were analyzed and compared to the incidence of fracture in the same period.</p> <p>Results and interpretation — The overall risk of non-union per fracture was 1.9%, which is considerably less than previously believed. However, for certain fractures in specific age groups the risk of non-union rose to 9%. As expected, these higher rates of non-union were observed with tibial and clavicular fractures, but—less expectedly—it was in the young and middle-aged adults rather than in the older and elderly population. This study is the first to examine fracture non-union rates in a large population according to age and site, and provides more robust (and lower) estimates of non-union risk than those that are frequently quoted.</p

Supercontinent-paced magmatic destabilisation and recratonisation of the Yilgarn Craton

Knowledge of the evolution of ancient cratonic lithospheres underpins our understanding of Precambrian Earth. The Yilgarn Craton has exceptionally well-preserved Archean geology, with juvenile crust formation and major orogenesis concluding in the Neoarchean, and a stabilised upper-crustal architecture developing before 2.42 Ga. However, in an apparent dichotomy, geophysical models resolve lithospheric mantle composition outside the range of xenolith data from Archean regions, indicating the lithospheric mantle has since been extensively refertilised. Post-Archean igneous and sedimentary rocks record a prolonged lithospheric evolution that is not well resolved in datasets recording bulk crustal isotopic evolution. Reconciling these, we combine interpretation of geological and geophysical data to resolve two phases of lithosphere destabilisation driven by major magmatic events at ∼2.06 Ga and at ∼1.08 Ga. During destabilisation, sub-lithospheric and sub-crustal mantle fluxes caused extensive mantle refertilisation. For 200–400 Ma post-refertilisation, distributed sedimentary basins formed during recratonisation of the now denser lithosphere. The timing of these events suggests a relationship with the early stages of supercontinent assembly: Dominant downwelling beneath the assembling supercontinent sustains a sufficiently non-tensile tectonic setting to inhibit lithospheric thinning and breakup and enhances lateral flow of any upwelling mantle. This setting allows widespread intraplate refertilisation to occur while later the assembled supercontinent provides a stable setting allowing thermal re-equilibration and recratonisation to occur. In contrast, lithospheric refertilisation during supercontinent breakup will be more susceptible to density instabilities and recycling in later collisions. Consequently, we suggest that refertilisation of extant cratonic lithosphere may dominantly have occurred during the assembly of supercontinents